US4236979A - Composite diaphragms and process for electrolyzing alkali metal chloride - Google Patents

Composite diaphragms and process for electrolyzing alkali metal chloride Download PDF

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Publication number
US4236979A
US4236979A US06/050,983 US5098379A US4236979A US 4236979 A US4236979 A US 4236979A US 5098379 A US5098379 A US 5098379A US 4236979 A US4236979 A US 4236979A
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US
United States
Prior art keywords
vinylpyridine
copolymer
divinylbenzene
weight
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/050,983
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English (en)
Inventor
Oronzio De Nora
Luigi Giuffre
Giovanni Modica
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Nora SpA
Original Assignee
Oronzio de Nora Impianti Elettrochimici SpA
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Publication of US4236979A publication Critical patent/US4236979A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2339/08—Homopolymers or copolymers of vinyl-pyridine

Definitions

  • the anodic compartment is separated from the cathodic compartment by a porous separator permeable to the electrolyte flow to keep the anodic gas (chlorine) separated from the cathodic gas (hydrogen) and to maintain the difference in pH existing between the anolyte and catholyte.
  • a porous separator permeable to the electrolyte flow to keep the anodic gas (chlorine) separated from the cathodic gas (hydrogen) and to maintain the difference in pH existing between the anolyte and catholyte.
  • Asbestos particularly chrysotile asbestos which is characterized by a tubular fiber structure and the formula 3 MgO.2SiO 2 . 2H 2 O has been, and still is, utilized for producing said diaphragms due to its particular property of resistance either in acidic environment or in strongly alkaline environment.
  • the said diaphragms are not dimensionally stable and tend to swell in the cell, sometimes up to 100%, getting so close to the anodic surface as to undergo an erosive action of chlorine gas bubbles evolved at the anode.
  • Another attempt at stabilizing asbestos diaphragms consists in codepositing asbestos fibers and preformed thermoplastic polymeric fibers or powder followed by a thermal treatment. This involves several problems because the high temperatures (200°-350° C.) necessary for the sinterization causes distortion of the metallic cathodic structure if a peculiar morphology of the same is not adopted, and a thermal degradation of the asbestos with formation of sodium silicate.
  • novel porous and electrolyte permeable composite diaphragms of the invention are comprised of a chemically inert, fibrous porous matrix or substrate impregnated with a copolymer of divinylbenzene and at least one member of the group consisting of 2-vinylpyridine and 4-vinylpyridine.
  • the copolymer is directly formed on the inert fibrous substrate in the absence of a solvent.
  • the advantages of the composite diaphragms of the invention are their great resistance to mechanical abrasion caused by brine flow and by chlorine bubbles. Their dimensional stability allows th inner diaphragms and smaller interelectrodic distances with a considerable saving of electric energy. Moreover, because the distance between the anode side of the diaphragm and the active surface may be accurately preset and is thereafter maintained, a better faraday efficiency together with a reduction of chlorate concentration in the catholyte is obtained even when operating with a higher caustic soda concentration in the catholyte.
  • the inert fibrous material is asbestos paper or asbestos mat, such as that produced by pulling a slurry of asbestos fibers through a foraminous metal electrode, but other fibrous inert materials may be used such as polyester fibers in the form of woven or unwoven felt or cloth and woven or unwoven carbon fiber felts.
  • the ratio of divinylbenzene to the vinylpyridine is 1/16 to 1/1, preferably between 1 to 9 and 2 to 3.
  • the composite diaphragm preferably contains 5 to 25% by weight of the final diaphragm of the said copolymer, most preferably 8 to 16% by weight.
  • the asbestos is made exceptionally stable and swelling and disintegration under the normal conditions of electrolysis of alkali metal halide brines are effectively prevented.
  • the diaphragm remains porous and permeable to brines up to a copolymer loading of about 25% of the total weight of the composite material.
  • the copolymer loading does not appear to make the fibrous matrix hydrophobic but rather it enhances its hydrophilic properties, making the composite material perfectly wettable by the electrolyte.
  • the pyridine group particularly in alkaline environments such as the occurring within the diaphragm in chlor-alkali cells, behaves as a negatively polarized group, because of the electron pair on the nitrogen atom thereof.
  • the novel method of the invention for the preparation of the composite diaphragm material comprises impregnating the inert fibrous matrix with a solution of 2.5 to 50% by volume of 2- and/or 4-vinylpyridine and divinylbenzene in an organic solvent such as benzene, toluene, xylene, acetone, etc.
  • a suitable polymerization initiator such as benzoylperoxide, or azobisisobutyronitrile
  • evaporating the organic solvent preferably at room temperature and under reduced pressure, heating the dried impregnated matrix at 75° to 100° C., preferably at 80° to 90° C. for a time sufficient to effect polymerization such as 2 to 4 hours under an inert atmosphere such as nitrogen, and washing the composite material with the organic solvent to remove unreacted monomers and low molecular weight copolymer.
  • the in situ copolymerization in the absence of an organic solvent produces a substantially uniform coating of the fibrous matrix and a strong bonding together of the fibers due to copolymer bridging between fibers resulting in an exceptionally strong material excellent resistance to swelling and erosion.
  • Permeability, porosity and wettability of the composite diaphragms prepared by the process of the present invention are prefectly reproducible characteristics which can be controlled by varying parameters such as the temperature and the time of polymerization and most of all, the concentration of the monomers in the soaking solution and their relative ratios.
  • the soaking solution may preferably contain from 10 to 25% of monomers and most preferably from 15 to 20% and the molar ratio (2) or (4) vinylpyridne/divinylbenzene may range from 16/1 to 1/1 and preferably from 9/1 to 3/2, giving to the copolymer an optimum cross-linking degree for good chemical resistance and sufficient hydrophilic properties to be wettable by the electrolyte.
  • the composite diaphragms of the invention are particularly useful in the electrolysis of alkali metal halide brines to produce the halogen and the alkali metal hydroxide such as chlorine and caustic soda but may also be used in other electrolysis reactions.
  • the novel electrolytic process of the invention for the preparation of a chemical product comprises providing an electrolyte containing the elements of the product to be produced in a electrolytic cell with an anode and a cathode separated by a porous, electrolyte permeable composite diaphragm made of chemical inert, fibrous porous matrix or substrate impregnated with a copolymer of divinylbenzene and at least one member of the group consisting of 2-vinylpyridine and 4-vinylpyridine, passing an electrolysis current through the anode, cathode and electrolyte and recovering said chemical product from the said cell.
  • the novel electrolytic cell of the invention comprises a cell housing containing at least one anode and at least one cathode forming an interelectrodic gap with a porous, electrolyte permeable diaphragm of the invention separating the anode and cathode.
  • the polymers may contain up to 30/40% molar percent of 1 or more other polymerizable monomers such as vinylacetate, methylmethacrylate or styrene.
  • the coated cathodic structures were then dried at 100° C. for three hours and were then soaked at room temperature in benzene solutions of 4-vinylpyridine and divinylbenzene at different concentrations and with different molar ratios of the monomers, as indicated in Table I.
  • the solutions also contained dibenzoyl peroxide as polymerization initiator of 1% molar with respect to the moles of the monomers. After evaporating the solvent under vacuum at room temperature, the exposed surfaces of the supporting cathodes were washed with benzene to avoid coating of the cathodic surfaces with the copolymer.
  • the cathode assemblies were then heated in a closed reactor designed to reduce to the minimum the space for the gas, at 80° C. for three hours. After cooling, they were washed with benzene to remove possible unreacted monomers.
  • the diaphragms, after drying, were weighed to determine the increase in weight of different amounts of 4-vinylpyridine/divinylbenzene copolymer as shown in Table I. They were then tested in pilot diaphragm cells for the electrolysis of sodium chloride, operating at the following conditions:
  • copolymer weight increases from 5 to 20% of the total weight of the diaphragm are effective in rendering it dimensionally stable, with elevated cathodic current efficiencies and not exceedingly high cell voltages.
  • a piece measuring 120 ⁇ 120 mm was cut from an asbestos sheet type 0.025 "L/FX 36" [produced by John Mainville & Co.] and it was soaked in a solution having the following composition by volume at 20° C.
  • Example 2 Using the technique of Example 1, the soaked asbestos sheet was heated in a reactor, with empty spaces reduced to the minimum, for 1 hour at 80° C. After cooling and flushing with toluene, the composite diaphragm showed a content of copolymer of 8.5% of its total weight. It was then tested in a diaphragm pilot cell for the electrolysis of sodium chloride having the following characteristics:
  • the cell voltage during the entire duration of the test varied from 3.2 to 3.4 V.
  • Example 2 Using the procedure of Example 2, a series of identical asbestos papers; 0.025 "L/FX 36" type made by John Mansville Co. were soaked with toluene solutions of 4-vinylpyridine and divinylbenzene at various concentrations and with different molar ratios of monomers to obtain diaphragms loaded with different copolymeric loadings as reported in Table III. The diaphragms were separately tested over a period of three weeks in chlor-alkali diaphragm cells, operating at the following conditions:
  • the diaphragm looses much of its permeability causing a rapid increase of the cell voltage.
  • the asbestos paper maintains a certain tendency to swell although in much reduced measure than an unloaded asbestos paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US06/050,983 1978-03-01 1979-02-22 Composite diaphragms and process for electrolyzing alkali metal chloride Expired - Lifetime US4236979A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT20792/78A IT1110461B (it) 1978-03-01 1978-03-01 Membrane anioniche costituite da copolimeri di (2) o (4)-vinilpiridina con divinilbenzene o con monomeri vinilici alogenati

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06/013,830 Division US4186076A (en) 1978-03-01 1979-02-22 Composite diaphragms

Publications (1)

Publication Number Publication Date
US4236979A true US4236979A (en) 1980-12-02

Family

ID=11172124

Family Applications (3)

Application Number Title Priority Date Filing Date
US06/050,983 Expired - Lifetime US4236979A (en) 1978-03-01 1979-02-22 Composite diaphragms and process for electrolyzing alkali metal chloride
US06/013,830 Expired - Lifetime US4186076A (en) 1978-03-01 1979-02-22 Composite diaphragms
US06/013,828 Expired - Lifetime US4221642A (en) 1978-03-01 1979-02-22 Anionic membranes

Family Applications After (2)

Application Number Title Priority Date Filing Date
US06/013,830 Expired - Lifetime US4186076A (en) 1978-03-01 1979-02-22 Composite diaphragms
US06/013,828 Expired - Lifetime US4221642A (en) 1978-03-01 1979-02-22 Anionic membranes

Country Status (6)

Country Link
US (3) US4236979A (enrdf_load_stackoverflow)
EP (2) EP0003851B1 (enrdf_load_stackoverflow)
JP (2) JPS54128981A (enrdf_load_stackoverflow)
CA (2) CA1144893A (enrdf_load_stackoverflow)
DE (1) DE2961044D1 (enrdf_load_stackoverflow)
IT (1) IT1110461B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0156422A1 (en) * 1984-03-16 1985-10-02 European Atomic Energy Community (Euratom) Composite diaphragms and process for alkaline water electrolysis

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Publication number Priority date Publication date Assignee Title
IT1113412B (it) * 1979-02-15 1986-01-20 Oronzio De Nora Impianti Procedimento eletttrolitico ed apparecchiatura per la preparazione di ipoalogenito di metallo alcalino
EP0033262B1 (fr) * 1980-01-29 1986-12-30 Elf Atochem S.A. Diaphragme pour électrolyse et son procédé de préparation
FR2505879B1 (fr) * 1981-05-15 1985-09-27 Chloe Chemie Diaphragme, son procede de preparation et le procede d'electrolyse le mettant en oeuvre
US4505797A (en) * 1983-03-24 1985-03-19 Ionics, Incorporated Ion-exchange membranes reinforced with non-woven carbon fibers
GB8522207D0 (en) * 1985-09-06 1985-10-09 Kodak Ltd Ion-sensitive electrochemical sensor
US4587269A (en) * 1985-09-16 1986-05-06 Ionics Incorporated One step process for preparing anion exchange polymers
US4647360A (en) * 1985-10-04 1987-03-03 The Dow Chemical Company Inert carbon fiber diaphragm
JPS61141905A (ja) * 1985-12-13 1986-06-28 Tokuyama Soda Co Ltd 電気透析方法
FR2645044B1 (fr) * 1989-03-30 1992-04-03 Morgane Membrane echangeuse d'ions pour electrodialyse et procede de recuperation d'acides mineraux mettant en oeuvre une telle membrane
JPH0642127A (ja) * 1992-07-21 1994-02-15 Nippon Steel Corp 屋根用幕板の伸縮継手構造
US6254978B1 (en) * 1994-11-14 2001-07-03 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
USRE37307E1 (en) 1994-11-14 2001-08-07 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
US6054230A (en) * 1994-12-07 2000-04-25 Japan Gore-Tex, Inc. Ion exchange and electrode assembly for an electrochemical cell
FR2740050B1 (fr) * 1995-10-24 1997-12-19 Solvay Procede de fabrication d'une membrane ambipolaire et membrane ambipolaire
US6635384B2 (en) * 1998-03-06 2003-10-21 Gore Enterprise Holdings, Inc. Solid electrolyte composite for electrochemical reaction apparatus
US6613203B1 (en) 2001-09-10 2003-09-02 Gore Enterprise Holdings Ion conducting membrane having high hardness and dimensional stability
MY162114A (en) * 2006-07-14 2017-05-31 Kao Corp Deodorant particle
US8079269B2 (en) * 2007-05-16 2011-12-20 Rosemount Inc. Electrostatic pressure sensor with porous dielectric diaphragm
KR20110019573A (ko) * 2009-08-20 2011-02-28 삼성전자주식회사 전기 흡착 탈이온 장치
KR101688530B1 (ko) * 2009-12-21 2016-12-21 삼성전자주식회사 전기 흡착 탈이온 장치
KR20110080893A (ko) * 2010-01-07 2011-07-13 삼성전자주식회사 탈이온 장치
US9861941B2 (en) * 2011-07-12 2018-01-09 Kraton Polymers U.S. Llc Modified sulfonated block copolymers and the preparation thereof
BR112015016565A2 (pt) 2013-01-14 2017-07-11 Kraton Polymers Us Llc copolímeros de bloco funcionalizado em amino ou fosfino, de bloco seletivamente halogenado, e de bloco precursor, membrana ou película, aparelho, conjunto de eletrodeionização, e, método para preparar o copolímero de bloco funcionalizado em amino ou fosfino
KR20220073842A (ko) * 2019-10-10 2022-06-03 크레이튼 폴리머스 엘엘씨 멤브레인 기반 에어 컨디셔닝 시스템

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US4036729A (en) * 1975-04-10 1977-07-19 Patil Arvind S Diaphragms from discrete thermoplastic fibers requiring no bonding or cementing
US4056447A (en) * 1975-03-06 1977-11-01 Oronzio De Nora Impianti Elettrochimici S.P.A. Electrolyzing alkali metal chlorides using resin bonded asbestos diaphragm

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US4036729A (en) * 1975-04-10 1977-07-19 Patil Arvind S Diaphragms from discrete thermoplastic fibers requiring no bonding or cementing

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0156422A1 (en) * 1984-03-16 1985-10-02 European Atomic Energy Community (Euratom) Composite diaphragms and process for alkaline water electrolysis

Also Published As

Publication number Publication date
IT7820792A0 (it) 1978-03-01
EP0003851B1 (en) 1981-10-21
IT1110461B (it) 1985-12-23
US4221642A (en) 1980-09-09
JPS54127883A (en) 1979-10-04
DE2961044D1 (en) 1981-12-24
EP0003851A2 (en) 1979-09-05
JPS5742712B2 (enrdf_load_stackoverflow) 1982-09-10
CA1144893A (en) 1983-04-19
US4186076A (en) 1980-01-29
CA1117716A (en) 1982-02-09
EP0003851A3 (en) 1979-09-19
EP0004029A1 (en) 1979-09-19
JPS54128981A (en) 1979-10-05

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